Oxidation by use of electronic atomic monolayer-metal support interaction catalysts

Abstract

Disclosed are catalysts that include a doped atomic monolayer (e.g., graphene or hexagonal boron nitride) bonded to a nickel-based component. The dopant can be a transition metal or nonmetal dopant and the nickel-based component can be pure nickel (e.g., Ni(111)) or nickel/metal alloys. Also disclosed are processes for catalyzing reactions that include adsorbing a small molecule to the catalyst and contacting the adsorbed small molecule with a reactant. Catalyzed reactions include oxidation reactions including oxidation of methane to methanol, oxidation of carbon monoxide (e.g., in a PROX reaction).

The invention claimed is: 
     
       1. A method for oxidation of methane to form methanol comprising:
 adsorbing oxygen on a catalyst, wherein the oxygen is chemisorbed on the catalyst, the catalyst comprising an atomic monolayer comprising graphene or hexagonal boron nitride, the catalyst further comprising a transition metal single atom dopant in a lattice of the atomic monolayer, wherein the atomic monolayer is covalently bonded to a surface of a support, the support comprising nickel (111) at the surface; 
 contacting the adsorbed oxygen with methane, upon which the methane is physisorbed on the catalyst and the methane is oxidized to form methanol. 
 
     
     
       2. The method of  claim 1 , wherein the method is carried out at a temperature of from about 350K to about 500K. 
     
     
       3. The method of  claim 1 , further comprising passing a fluid comprising the methane over the catalyst. 
     
     
       4. The method of  claim 3 , wherein the method comprises only a single pass of the fluid over the catalyst. 
     
     
       5. The method of  claim 1 , wherein the transition metal single atom dopant is scandium (Sc), titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), yttrium (Y), zirconium (Zr), niobium (Nb), molybdenum (Mo), technetium (Tc), ruthenium (Ru), rhodium (Rh), palladium (Pd), silver (Ag), cadmium (Cd), hafnium (Hf), tantalum (Ta), tungsten (W), rhenium (Re), osmium (Os), iridium (Ir), platinum (Pt), gold (Au), or mercury (Hg). 
     
     
       6. The method of  claim 5 , wherein the transition metal single atom dopant is Cu, Rh, Fe, Ir, or Mn. 
     
     
       7. The method of  claim 5 , wherein the transition metal single atom dopant is Cu or Rh. 
     
     
       8. The method of  claim 1 , wherein the atomic monolayer comprises graphene. 
     
     
       9. The method of  claim 8 , wherein the graphene comprises graphene featuring a MN4 motif. 
     
     
       10. The method of  claim 1 , wherein the atomic monolayer comprises hexagonal boron. 
     
     
       11. The method of  claim 10 , wherein the transition metal single atom dopant is inserted at a boron vacancy. 
     
     
       12. The method of  claim 10 , wherein the transition metal single atom dopant is inserted at a nitrogen vacancy. 
     
     
       13. The method of  claim 1 , wherein the support comprises greater than 50 atomic % of the nickel (III). 
     
     
       14. The method of  claim 13 , wherein the support comprises one or more additional metals. 
     
     
       15. The method of  claim 1 , wherein the support is in the form of a particulate. 
     
     
       16. The method of  claim 15 , wherein the support comprises greater than 50 atomic % of the nickel (III). 
     
     
       17. The method of  claim 16 , wherein the support comprises one or more additional metals.